CN110304996B - Method for removing alkali catalyst - Google Patents
Method for removing alkali catalyst Download PDFInfo
- Publication number
- CN110304996B CN110304996B CN201910575430.9A CN201910575430A CN110304996B CN 110304996 B CN110304996 B CN 110304996B CN 201910575430 A CN201910575430 A CN 201910575430A CN 110304996 B CN110304996 B CN 110304996B
- Authority
- CN
- China
- Prior art keywords
- reaction system
- reaction
- carbon dioxide
- alcohol
- alkali catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
- A23D7/02—Edible oil or fat compositions containing an aqueous phase, e.g. margarines characterised by the production or working-up
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for removing an alkali catalyst, which comprises the following steps: and introducing carbon dioxide into the organic reaction system to generate a solid, and then removing the solid to realize the removal of the alkali catalyst. According to the invention, carbon dioxide is introduced into the system, and the carbon dioxide reacts with the base catalyst to generate carbonate and/or bicarbonate, wherein the carbonate and/or bicarbonate cannot be dissolved in the organic reaction system and is precipitated in a solid form, and the target product of the organic reaction is still dissolved in the reaction system. The invention can realize the removal of the alkali catalyst by removing the solid in the reaction system. The method provided by the invention can effectively remove the alkali catalyst in the reaction system, and has zero emission and no loss to products.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for removing an alkali catalyst.
Background
In the esterification reaction and the polymerization reaction, the catalyst used is mostly an alkali catalyst, for example, the catalyst for the transesterification reaction, the polymerization of glycerin to prepare polyglycerin, etc. is generally sodium hydroxide or potassium hydroxide. In the above reaction, after the reaction is completed, it is necessary to remove the catalyst from the reaction system and further separate it to obtain the desired product.
In the prior art, the method for removing the alkali catalyst is generally to add acid for neutralization and then wash with water. The method comprises the steps of firstly, discharging waste water, and secondly, after products are neutralized and washed, vacuum dehydration is needed to remove water in the materials; thirdly, in the washing process, a small amount of products can be discharged together with the washing water, so that the product loss is caused; fourthly, the dosage of the acid needs to be strictly controlled, and if the acid is excessive, the product quality of the product is unqualified or the product is lost due to the increase of water washing.
Disclosure of Invention
The invention provides a method for removing an alkali catalyst, which is simple, does not need water washing, and does not cause product loss.
The invention provides a method for removing an alkali catalyst, which comprises the following steps:
and introducing carbon dioxide into the organic reaction system to generate a solid, and then removing the solid to realize the removal of the alkali catalyst.
Preferably, the base catalyst includes one of sodium hydroxide, potassium hydroxide, sodium methoxide and sodium ethoxide.
Preferably, the organic reaction system is a transesterification reaction system, an ester-alcohol exchange reaction system or an alcohol-alcohol polymerization reaction system.
Preferably, the transesterification reaction system comprises transesterification reaction of grease and grease; the ester-alcohol exchange reaction system comprises ester-alcohol exchange reaction of grease and alcohol substances; the alcohol-alcohol polymerization reaction system includes a glycerol polymerization reaction.
Preferably, the organic reaction system is an organic reaction system after the reaction of the raw materials is completed; the organic reaction system does not contain water.
Preferably, the temperature of the organic reaction system is less than or equal to 100 ℃.
Preferably, the introduction amount of the carbon dioxide is controlled by the pH value of the reaction solution, and when the pH value of the reaction solution is 6.8-7.2, the introduction of the carbon dioxide is stopped.
Preferably, the carbon dioxide is introduced from the bottom of the reaction apparatus while stirring.
Preferably, the solids are removed by filtration or centrifugation followed by supernatant removal.
Preferably, the filtration is filter pressing or suction filtration.
The invention provides a method for removing an alkali catalyst, which comprises the following steps: and introducing carbon dioxide into the organic reaction system to generate a solid, and then removing the solid to realize the removal of the alkali catalyst. According to the invention, carbon dioxide is introduced into the system, and the carbon dioxide reacts with the base catalyst to generate carbonate and/or bicarbonate, wherein the carbonate and/or bicarbonate cannot be dissolved in the organic reaction system and is precipitated in a solid form, and the target product of the organic reaction is still dissolved in the reaction system. The invention can realize the removal of the alkali catalyst by removing the solid in the reaction system. The method provided by the invention can effectively remove the alkali catalyst in the reaction system, and has zero emission and no loss to products.
Detailed Description
The invention provides a method for removing an alkali catalyst, which comprises the following steps:
and introducing carbon dioxide into the organic reaction system to generate a solid, and then removing the solid to realize the removal of the alkali catalyst.
In the present invention, the base catalyst preferably includes one of sodium hydroxide, potassium hydroxide, sodium methoxide and sodium ethoxide.
In the present invention, the organic reaction system is preferably an ester exchange reaction system, an ester alcohol exchange reaction system, or an alcohol polymerization reaction system. In the present invention, the catalyst of the organic reaction system is preferably sodium hydroxide and/or potassium hydroxide.
In the present invention, the transesterification reaction preferably includes a transesterification reaction of a fat and an oil, and more preferably includes a transesterification reaction of a solid oil and a liquid oil. In the present invention, the solid oil is preferably a hydrogenated oil obtained by hydrogenating a liquid oil; the liquid oil is preferably refined liquid vegetable oil, and is more preferably refined edible oil. In the present invention, the main purpose of the refining is deodorization and decolorization, and the refining method of the present invention is not particularly limited, and a refining method known to those skilled in the art may be used. In the present invention, in the transesterification reaction system, it is preferable that after the completion of the transesterification reaction, the temperature of the reaction system is lowered to 100 ℃ or lower, 0 ℃ or higher, more preferably 90 ℃ or lower, 10 ℃ or higher, still more preferably 80 ℃ or lower, 20 ℃ or higher, and then carbon dioxide is introduced. According to the invention, the reaction system is preferably cooled and then carbon dioxide is introduced, so that solid can be fully precipitated in the subsequent process, and the alkali catalyst in the reaction system can be more fully and completely removed.
In the present invention, the alcohol ester exchange reaction preferably includes an ester alcohol exchange reaction of the grease with an alcohol substance, and the alcohol substance preferably includes one or more of ethylene glycol, propylene glycol, glycerol, pentaerythritol, neopentyl glycol, triethylene glycol, butanol, octanol, and fatty alcohol; the alcohol transesterification reaction further preferably comprises the reaction of a fatty acid triglyceride with glycerol. In the present invention, after the completion of the transesterification reaction, the temperature of the reaction system is preferably lowered to 100 ℃ or lower, 0 ℃ or higher, more preferably 90 ℃ or lower, 10 ℃ or higher, still more preferably 80 ℃ or lower, 20 ℃ or higher, and then carbon dioxide is introduced.
In the present invention, the alcohol polymerization reaction system preferably includes glycerin polymerization reaction and ethylene glycol polymerization reaction. In the alcohol polymerization reaction system, in the present invention, after the completion of the alcohol polymerization reaction, the temperature of the reaction system is preferably lowered to 100 ℃ or lower, 0 ℃ or higher, more preferably 90 ℃ or lower, 10 ℃ or higher, still more preferably 80 ℃ or lower, 20 ℃ or higher, and then carbon dioxide is introduced.
In general, transesterification and polymerization of alcohol are carried out at a temperature higher than 100 ℃ and water in the reaction system is removed during the reaction. The organic reaction system is preferably an organic reaction system after the reaction of the raw materials is finished, so that the organic reaction system does not contain water.
The invention leads carbon dioxide into an organic reaction system to generate solid. In the present invention, the amount of carbon dioxide to be introduced is preferably controlled by the pH of the reaction solution, and when the pH of the reaction solution is preferably 6.8 to 7.2, more preferably 6.9 to 7.1, and even more preferably 7, the introduction of carbon dioxide is stopped. In the invention, the introduced carbon dioxide reacts with an alkali catalyst to generate carbonate and/or bicarbonate; the carbonate and the bicarbonate can not be dissolved in the organic reaction system without water at the temperature of less than 100 ℃, and are separated out in a solid form, and the target product of the organic reaction is still dissolved in the reaction system. In the present invention, the solid is preferably one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate. In the invention, the excessive carbon dioxide enters the water seal tank after coming out of the reaction device and is dissolved in water to generate carbonic acid, thereby achieving zero emission. In the invention, carbon dioxide is preferably introduced from the bottom of the reaction device and stirred at the same time, which is beneficial to the full reaction of the carbon dioxide and the alkali catalyst. In the invention, when the method is applied to industry, the carbon dioxide is preferably introduced at a speed of 60-80L/min; when the method is applied to a laboratory, the introducing speed of the carbon dioxide is preferably 40-80 mL/min, and more preferably 50-70 mL/min. The invention preferably controls the carbon dioxide feeding speed in the range, which is beneficial to fully reacting the carbon dioxide with the alkali catalyst and accurately controlling the dosage of the carbon dioxide.
According to the invention, after carbon dioxide is introduced, the reaction system can be in a turbid state, namely, carbonate (or bicarbonate) exists. According to the invention, preferably, after the carbon dioxide is introduced, the reaction system is subjected to standing treatment to precipitate solid matters in the reaction system so as to remove the solid matters subsequently and obtain supernatant. In the invention, the standing treatment time is preferably 10-20 h.
The invention removes solid and realizes the removal of the alkali catalyst. In the present invention, the mode of removing solids is preferably filtration, more preferably filter pressing, and still more preferably plate and frame filter pressing. After removing solids, collecting filtrate, wherein the filtrate is a target product of an organic reaction system. The subsequent treatment mode of the filtrate is not particularly required by the invention, and the treatment mode known by the technicians in the field can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
276g of pure glycerol and 1.4g of sodium hydroxide serving as a catalyst are respectively added into a reaction bottle, stirring is started simultaneously, nitrogen is introduced, glycerol polymerization reaction is carried out to prepare triglycerol, the reaction temperature is 245 ℃, about 36g of reaction water is discharged, the reaction is finished, the temperature is reduced to 80 ℃, the pH value of the reaction system is measured to be 9 by a pH measuring instrument for sampling, carbon dioxide gas is introduced, about 1.5L of carbon dioxide gas is metered, the reaction is finished, and the pH value of the reaction system is measured to be 7.2 by a pH measuring instrument for sampling. The reaction material liquid is subjected to pressure filtration (or high-speed centrifugation) to obtain a target product.
Note: the unreacted carbon dioxide from the reaction bottle enters a water-sealed bottle and is dissolved in water to generate carbonic acid.
Example 2
300g of tristearin, 60g of pure glycerol and 1.5g of catalyst sodium hydroxide are respectively added into a reaction bottle, stirring is started simultaneously, nitrogen is introduced, and the reaction is carried out to prepare the glyceryl monostearate and the glyceryl distearate, wherein the reaction temperature is 215 +/-5 ℃, and the reaction time is 2 hours. And (3) finishing the reaction, cooling to 90 ℃, sampling, measuring the pH value of the reaction system to be 8.5 by using a pH measuring instrument, introducing carbon dioxide gas, measuring about 1.6L of the introduced carbon dioxide gas, finishing the reaction, and sampling, measuring the pH value of the reaction system to be 7 by using the pH measuring instrument. And filtering the reaction feed liquid to obtain a target product.
Note: the unreacted carbon dioxide from the reaction bottle enters a water-sealed bottle and is dissolved in water to generate carbonic acid.
Example 3
Adding 800kg of glyceryl tristearate, 200kg of pentaerythritol and 4.5kg of sodium hydroxide into a reaction kettle respectively, starting stirring simultaneously, introducing nitrogen, and carrying out ester-alcohol exchange reaction to prepare the pentaerythritol glyceryl stearate composite ester. Reacting at 225 + -5 deg.C for 150min, finishing the reaction, and cooling to 100 deg.C. And (3) sampling, measuring the pH value of the reaction system to be 8.5 by using a pH measuring instrument, introducing carbon dioxide gas for about 60min, measuring the reaction, introducing about 4.5 cubic degrees of carbon dioxide gas, finishing the reaction, and measuring the pH value of the reaction system to be 6.8 by using the pH measuring instrument. And filtering the reaction feed liquid to obtain a target product.
Note: and the unreacted carbon dioxide from the reaction kettle enters a water seal tank and is dissolved in water to generate carbonic acid.
Example 4
280g of tristearin (namely hydrogenated oil), 120g of refined edible oil and 1.6g of sodium hydroxide (which are melted by a small amount of water) are respectively added into a four-mouth round-bottom reaction bottle, nitrogen is introduced, and ester exchange reaction is carried out to prepare the margarine with the melting point of 38-40 ℃. Controlling the reaction temperature at 160 ℃, reacting for 180min, finishing the reaction, and cooling to 60 ℃. And (3) sampling, measuring the pH value of the reaction system to be 8.5 by using a pH measuring instrument, introducing carbon dioxide gas, controlling the flow rate to be 65mL/min, controlling the time to be about 30min, introducing about 2L of carbon dioxide gas in a reaction metering manner, finishing the reaction, and measuring the pH value of the reaction system to be 7 by using the pH measuring instrument. And filtering the reaction feed liquid to obtain a target product. The melting point of the product was determined to be 38 ℃.
Note: and the unreacted carbon dioxide from the reaction kettle enters a water-sealed bottle and is dissolved in water to generate carbonic acid.
In conclusion, the method provided by the invention can effectively remove the alkali catalyst in the reaction system, and has zero emission and no loss to products.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A method for removing an alkali catalyst comprises the following steps:
introducing carbon dioxide into the organic reaction system to generate a solid, and then removing the solid to realize the removal of the alkali catalyst;
the alkali catalyst comprises one of sodium hydroxide, potassium hydroxide, sodium methoxide and sodium ethoxide;
the organic reaction system is an ester exchange reaction system, an ester-alcohol exchange reaction system or an alcohol-alcohol polymerization reaction system;
the ester exchange reaction system comprises ester exchange reaction of grease and grease; the ester-alcohol exchange reaction system comprises ester-alcohol exchange reaction of grease and alcohol substances; the alcohol-alcohol polymerization reaction system comprises glycerol polymerization reaction;
the organic reaction system is an organic reaction system after the raw material reaction is finished; the organic reaction system does not contain water;
the temperature of the organic reaction system is less than or equal to 100 ℃;
the introduction amount of the carbon dioxide is controlled by the pH value of the reaction liquid, and when the pH value of the reaction liquid is 6.8-7.2, the introduction of the carbon dioxide is stopped;
introducing carbon dioxide from the bottom of the reaction device, and stirring simultaneously;
the carbon dioxide is introduced at a speed of 60-80L/min;
the solid removal mode is filtering or centrifuging and then taking supernatant liquor;
the filtration is filter pressing or suction filtration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910575430.9A CN110304996B (en) | 2019-06-28 | 2019-06-28 | Method for removing alkali catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910575430.9A CN110304996B (en) | 2019-06-28 | 2019-06-28 | Method for removing alkali catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110304996A CN110304996A (en) | 2019-10-08 |
| CN110304996B true CN110304996B (en) | 2022-02-11 |
Family
ID=68078570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910575430.9A Active CN110304996B (en) | 2019-06-28 | 2019-06-28 | Method for removing alkali catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110304996B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115582112A (en) * | 2022-10-19 | 2023-01-10 | 浙江锦润生物科技有限公司 | Composite catalyst and application thereof in esterification reaction or ester exchange reaction |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157598A (en) * | 2006-11-09 | 2008-04-09 | 北京格瑞华阳科技发展有限公司 | Process for improving product quality and yield of propanediol and glycol |
| WO2011008847A2 (en) * | 2009-07-14 | 2011-01-20 | Ceramatec, Inc. | Systems and methods for removing catalyst and recovering free carboxylic acids from transesterification reaction |
| CN104043480A (en) * | 2014-05-09 | 2014-09-17 | 天津大学 | Ionic liquid catalyst and dimethyl carbonate synthesis method |
| CN104447312A (en) * | 2014-11-21 | 2015-03-25 | 常州大学 | Dimethyl carbonate synthesis method |
| CN105344341A (en) * | 2015-10-26 | 2016-02-24 | 常州大学 | Preparation method of solid catalyst used for synthesizing dimethyl carbonate |
| CN106588657A (en) * | 2016-11-10 | 2017-04-26 | 常州大学 | Method for synthesizing dimethyl carbonate |
| CN106588658A (en) * | 2016-11-18 | 2017-04-26 | 常州大学 | Method of synthesizing dimethyl carbonate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8247585B2 (en) * | 2009-07-14 | 2012-08-21 | Ceramatec, Inc | Systems and methods for removing catalyst and recovering free carboxylic acids after transesterification reaction |
-
2019
- 2019-06-28 CN CN201910575430.9A patent/CN110304996B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157598A (en) * | 2006-11-09 | 2008-04-09 | 北京格瑞华阳科技发展有限公司 | Process for improving product quality and yield of propanediol and glycol |
| WO2011008847A2 (en) * | 2009-07-14 | 2011-01-20 | Ceramatec, Inc. | Systems and methods for removing catalyst and recovering free carboxylic acids from transesterification reaction |
| CN104043480A (en) * | 2014-05-09 | 2014-09-17 | 天津大学 | Ionic liquid catalyst and dimethyl carbonate synthesis method |
| CN104447312A (en) * | 2014-11-21 | 2015-03-25 | 常州大学 | Dimethyl carbonate synthesis method |
| CN105344341A (en) * | 2015-10-26 | 2016-02-24 | 常州大学 | Preparation method of solid catalyst used for synthesizing dimethyl carbonate |
| CN106588657A (en) * | 2016-11-10 | 2017-04-26 | 常州大学 | Method for synthesizing dimethyl carbonate |
| CN106588658A (en) * | 2016-11-18 | 2017-04-26 | 常州大学 | Method of synthesizing dimethyl carbonate |
Non-Patent Citations (4)
| Title |
|---|
| 甘油深加工研究进展;许元栋等;《农业机械》;20111231(第14期);第64-67页 * |
| 聚甘油及其衍生物的合成与应用;马增欣，阚以翠;《石油化工》;19961120(第11期);第793-799页 * |
| 聚甘油脂肪酸酯合成与应用;聂凌鸿;《粮食与油脂》;20030110(第01期);第46-47页 * |
| 酯交换法1,2-丙二醇产品质量及收率的研究;滕文彬等;《山东化工》;20100815(第08期);第20-22页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110304996A (en) | 2019-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6586212B1 (en) | Corn fiber for the production of advanced chemicals and materials: derivatizable cellulose and cellulose derivatives made therefrom | |
| US6127560A (en) | Method for preparing a lower alkyl ester product from vegetable oil | |
| US4164506A (en) | Process for producing lower alcohol esters of fatty acids | |
| CA1155113A (en) | Process for recovery of polyol fatty acid polyesters | |
| US11242650B2 (en) | Methods and systems for solvent purification | |
| CA2430188C (en) | Method for pretreating crude oils and raw fats for the production of fatty acid esters | |
| KR20080015758A (en) | Production of biodeisel and glycerin from high free fatty acid feedstocks | |
| CN111094312B (en) | Preparation method of sucrose ester | |
| CN110304996B (en) | Method for removing alkali catalyst | |
| EP0566047A2 (en) | Process for producing carboxylic acid ester | |
| EP2316913B1 (en) | A Method Of Converting Free Fatty Acid (FFA) From Oil To Methyl Ester | |
| CN105419939A (en) | Fixed bed decolorization process of polyunsaturated fatty acid | |
| JP2002522627A (en) | Method for purifying fatty substances | |
| JPWO2008078769A1 (en) | Method for producing fatty acid lower alkyl ester | |
| CN102924409B (en) | Refining method of vitamin C | |
| CN105647982B (en) | The method of paddling process Enzyme catalyzed synthesis Ascorbyl Palmitate is combined under Ultrasonic Conditions | |
| CN221580605U (en) | Decolorization and desalination system based on mannitol oleate mixture | |
| CN114832758B (en) | Production method of low-color diisobutyl phthalate with activated carbon removed | |
| RU2281320C2 (en) | Process of producing oil from oil-containing vegetable raw material, process of extraction and refinement thereof, and apparatuses for implementation the same | |
| CN114149322A (en) | Preparation process of medium-chain fatty acid mono-diglyceride | |
| SU870395A1 (en) | Method of producing nitroacetic acid salts | |
| KR20040007311A (en) | A method for producing a fatty acid | |
| JPH0724589B2 (en) | Refining method of high acid value oil | |
| CN116693390A (en) | Composition of cetostearyl alcohol and fatty acid, and preparation method and application thereof | |
| CN118206605A (en) | Method for extracting cholesterol from fish oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A Method of Removing Alkali Catalyst Effective date of registration: 20221026 Granted publication date: 20220211 Pledgee: Zhejiang Fuyang Rural Commercial Bank branch of the new Limited by Share Ltd. Pledgor: ZHEJIANG JINRUN BIOTECHNOLOGY CO.,LTD. Registration number: Y2022980019748 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |